Dentifrice and method of making the same.



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Be it known that we, WILLIAM-1F. SPIES,

a citizen of thelUnited States, and resident of New York city, county mismaof New York, and HERBERT l1. PnAsn, a. citizen of the United States, and resident of Richmond Hill, county of Queens, and State of New York, have invented 'certainnew and useful Improvements in Dentifrices and Methods.

tages for other cleansing, absorbing, antiseptic or germicidal purposes.

When the powder is used alone its non abrasive, frictional cleansing properties and.

ability to absorb and give off fluids are available and where the powder is combined with "plastic material to make a tooth paste, or with adhesive bindln tablet, the same desira le qualities are available in combination with others which will be explained hereinafter.

Heretofore tooth powders and pastes. have "usually contained soap. flavoring ex tracts, antiseptics or mild gemnicides, together with a powdered material adapted to have a scouring effect when rubbed upon the teeth. Our experiments show that the precipitated .chalk'ipowder commonlyused for such purposes acts as an abrasive, thecut-ting action of which is shown by marked grooves in the teethwhen applied to themwlth brush. and

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water. Any other material having the ability to remove hardened deposit or tartar wouldalso have the ability to abrade theas contrasted with this, our invention recognizes that the ordinary tooth brush user should not employ a dentifrice whichwill do more than prevent or retard the formationof tartar by keeping his teeth free from food and tartar forming seci etions; that" rematerial to make a' specification-of Iletters Patent. Patented Aug. 13,1918. Application filed December so, 1917. Serial No. aoaoea. 3

moving tartar is a special operation for which a dentist should be regularly employed; and that a dentifrice suitable for general usecanbe and'should belfree from combination with soap, antiseptics. or ger micides. As compared with chalk, its advantageous qualities include a difi erent and superior land of mechanical cleaning action and a superior and probably did'erent action as an absorber and carrier of the antiseptics, germicides' and other'ingredients of the dentifrice.

.We have discovered and practically dem onstrated that solidified, substantially nonstructural cellulose powder can be prepared according to methods devised by us so that it will have peculiar frictional qualities whereby when rubbed along the tooth surfaces, the

- material clings to and efiectively cleans the surfaces without abradin them. It takes up mucus and otherdisc arges by absorption and also by adsorption, that is, by

clinging to the surfaces of the cellulose. It I has a similar non-abrasive cleaning action on metals.

- A solidified, substantially non-structural cellulose suitable for our purpose may be prepared in various. ways but we prefer only those methods which will result in minute particles of solid, horn-like carbohydrate, preferably one which will be of greater or less hardness accordin to the per- 'curdlike precipitate from a carbohydrate solution such as fresh, thoroughly converted viscose. Thismay be accomplished by rendering the solvent non-solvent as by the action of suitable acid salt solutions as'for in- "stance, sodium bisulfite or. calcium chlorid,

- or both of-them in approximately equal quantities. The cellulose thus freed from solution may be condensed to the desired a physical condition by freein it from some the admixed water and reaking it up to small particles before it hardens. The precipitate usually contains undesirable impurities which give a yellow color. These mpurities are more or less completely removed by repeated" washing with water,

' m'ately pure product which results from the should be observed.

which may. be rendered slightly alkaline by adding a small amount of bicarbonate of,

soda. or equivalent. This is sometimes de-' sirable because of the difficulty in completely removing the acid by the washing and a slight alkaline quality in the product s preferable to the acid quality. The approxifinal washing is dried and ground, preferably to a very fine powder, preferably not the process include the making of the viscose as ,well as the subsequent precipitating of the cellulose hydrate.

The raw material which we'use is pref-- erably white paperpulp made from wood by the sul-fite process. To one pound of this pulp torn into fine bits, add two pounds of caustic soda dissolved in six pounds of water, let it stand for an hour or so with -=occasional stirring, press to a dry cake,

break up the cake, add eight ounces of carbon disulfid in an air-tight tank, allow the process of conversion into soluble cellulose to continue from two to eight hours. The progress of the reaction may be judged by the successive colors,- brown, russet-brown,

orange and yellow and by the solubility of the material in water. Over-treatment, at this stage of the making of the viscose-is to be avoided since it may adversely affect I the final product. Since over-treatment does not decrease the solubility, the time to discontinue the treatment is when repeated solubility tests show that the cellulose has just become fully converted and completely soluble in water. The converted cellulose is then dissolved in thirty pounds of water.

To the resulting viscose solution amounting to-forty-six pounds more or less, is added about six ounces of concentrated, say 50% solution of calcium chlorid, and six ounces or more of sodium bisulfite (probably somewhat stronger than fifty per cent). Preffield of the microscope one or more erably, these are mixed cold. The effect is to convert the'viscose into a thick gelatin-like mass which" appears to consist of the cellulose precipitated'but not separated, the water in which it was dissolved remaining uniformly difi'used and mixed with the cellulose. The same or even better result may be produced by usin twelve to fifteen ounces of the sodium. isulfite without the calcium chlorid. The thick gelatin-like r'oduct which results in either case may e further thickened in any desired way.

One way is to boil it at a-low heat with continuous agitation, the result being a smooth, fine mixture from which fine grain particles of the cellulose readily settle out. Another way is to permit the mixture to stand, the cellulose content will then gradually contract, expelling water and with it many" of the undesirable impurities. In so doing, it shrinks away from the sides of the container and becomes more and more like solidified gelatin. When the latter stage is reached, the expelled water may be poured off and the gelatin-like mass broken up by hand, or otherwise, to a desired degree of fineness.

The gelatin-like particles produced by either the boiling or the settling method are repeatedly washed and the water strained off through a cloth until the material of the particles are substantially clean.

Washing should be continued for some time after the solution and the substance appear to be clean, a satisfactory degree of cleanness being determinable by the iodin test. Dilute tincture of iodin, when applied either'to the wash water or to the powder either wet or dry,.wi1l lose its color if the impurities are still present but will not lose its color if the product has been sufficiently washed.

After final washing, the cellulose particles are dried and ground. Preferably, they are first dried just enough for easy grinding and after grinding, are further dried to the. hardness required in the final product. If desired, however, all of the drying may be done before grinding.

The solidified material whether wet or dry is practically clean cellulose which is mainly non-structural and which usually contains more or less water. individual particles are translucent, the powder is almost white with a slight creamy tinge. The particles appearv under the microscope as being of more or less irregular structure. Often, there will be visible in the articles of unbroken down fibers. This, .ike other structural material, will be found lacking in some of the desirable physical and chemical qualities of the non-structural cellulose hydrate, and though we prefer to conduct the process so as to have as little as Though the till dll

possible of the structural material, it is nevertheless possible to leave or even to in troduce considerable quantities of structural material precipitated in the particles nroa vided it 1s incorporated with sumcient lli removed calcium content is an appreciable ercentage, the substance may be made quite hard, prelerably'not much harder than the substance of the teeth, for such hardness would result in the abrasive action whichis undesirable tor dentifrices though it may be desired for other purposes, as for instance, cleaning metal.

ln the pure product the hardness and frictional cleaning qualities, as well as the ability of the material to absorb and give 0 water, antiseptics, germicidesand medicaments, and to take upjmucus and other 'mouth secretions, mayvbe'varied within aconsiderable range by varying the water content of the material. lln general, the less water the material contains, the harder and more inert it seems to be. While the variability of the material in this respect seems to be more'or less uniformly progressive with progressive changes of its Water 7 content, it is well to note certain characteristic conditions of the material.

- Drying as by yexposure to the atmosphere at temperatures ay 80 to 100 centigrade,

serves to drive ofi more or less of the me. 'chanically absorbed moisture -the materlal retaining some 12% to 15% of water which at a'ppearsto be chemically combined in the molecules of the cellulose and so justifying the description of the material-as non-structural cellulose hydrate.- The water of combination may be'driven ofi, however, and a to dehydrated non-structural .cellulose produced by continuing thefdrying for a suifi:

cient time at temperatures up to or slightly above 130 centigrade.

The dehydrated cellulose will chemically recombine with water to produce the cellulose hydrate and thecellulose hydrate will absorb additional water without chemical combination, up to say 40% to of the a fllm form on the surfaces of the particles and By conducting the process so that the 1111- becoming wet, that is by taking up water in in theinarrow spaces adjacent their points of contact. In this condition, it may' be called wet non-structural cellulose. lit the powder thus wetted is the dehydrate or the dry hydrate the material ofthe particles 0 .will ultimately absorb enou h water to the powder is again moistened.

The. above described physical and chemi-' a5 cal properties 1 render the powder particularly useful for cleansing or polishing by friction without abrasion and also'as a new tra'l adsorbent and carrier for germicides,

antiseptics and medicines. Both qualities are utilized to the fullest extent where the powder is employed for our primary purpose, namely, as the basis for a non-abrasive germicide or antisepticdentifrice.

Our dentifrice is made by impregnating lib the finely ground non-structural cellulose powder with the antiseptic germicide or medicament in any desired way, as for instance, by discharging an atomizing spray of the liquid into or over a movingstream 10a of the powder and stirring the latter so asto uniformly distribute the germicide. Desired ingredients may be distributed with more perfect uniformity by diluting them or by wettingor moistening the powder.- In 10a either'case the impregnated powder may be 7 dried andmay be sieved or even reground if necessary to restore the required fineness of 7 grain. I I

Any suitable germicide or medicament may be used, as for instance, the well known coal tar germicides such as phenols, icresols or Xylenols, either with or without a flavoring, odorant or perfuming medium. i

The above as well as many other germi- 1 cides are primarily of an oily nature and moistening method is suitable for applying the emulsified antiseptics while the dry pow- 12o der method is more suitable for the oily forms.

The. emulsified disinfectants exhibit the greater germ' killing power because] of the greater availability of small microscopic E globules of the relatively insoluble germicide inmixture with water as contrasted with the relatively large droplets of the un-emulsified oil. The emulsified disinfectants maybe made with various emulsifying agents.

pregnated gelatin, gums and water solubleoil may be employed. v We" may employ germicides and antisepticsother than those above named, as for instance, alcohols; also oils that have been im-' with antise tics particularly 1 those in gaseous form suc as formaldehyde gas dissolved in essential oil, chlorin gas dis solved ,in arafiin oil; also essential oils such as oil ofv avender, bergamot, etc.

Although the word antiseptic applies I more accurately to material that-merely reterm to include germicides and ,disinfectants which prevent the growth of bacvents the growth .of bacteria without kil ing them, we elect to use it herein'as. a. generic I teria because they do kill them.

Our non-structural cellulose powder,

though acting perfectly as a frictional cleanser, causes noperceptible abrasion or wear and is a perfect carrier for the germicides and medicaments. Even in a dry state it retains the antiseptic in active condition and when moistened, it readily gives up the antiseptic with its sterilizing qualities unim paired. a

We claim:

1. A frictional cleaning medium comprising'finely comminuted non-structural cellulose hydrate.

'2. A dentifrice comprising non-structural cellulose hydrate in the form of small, nonabrasive, water absorbent, oil adsorbent particles.

3. A dentifrice comprising non-structural cellulose inth'e form of small, non-abrasive, water absorbent, oil adsorbent particles impregnated with an antiseptic,

4. A dentifrice comprising non-structural cellulose in the form of small, non-abrasive,

water absorbent, oil adsorbent particles imminuted particles containing substantially non-structural cellulose impregnated with an emulsified oily antiseptic. 6. A dentifrice comprising finely c0mminuted particles containing substantially non-structural cellulose impre ,ated with an emulsified oily disinfectant erived from coal tar,

7. A dentifrice comprising finely comminuted particles containing substantially non-structural cellulose slightly alkaline and impregnated with emulsified xylenol.

' 8. A dentifrice comprising finely com minuted particles containing precipitated, substantially non-structural cellulose impregnated with an emulsified oily antiseptic.

9. A dentifrice comprising finely comminuted particles containing precipitated, substantially non-structural cellulose impregnated with an emulsified oily disinfectant derived from coal tar.-

to purifythe material an soapis the most commonly emplo edibut 10.--'A chemically neutral and stable non- 12. A product having antiseptic proper-' ties comprising a finely comminuted nonstructural cellulose impregnated with an antiseptic.

13. A product having antiseptic properties comprising comminuted, substantially non-structural cellulose particles im regnated with an emulsified oily antiseptic.

14. A product having antiseptic properties comprising comminuted, substantially non-structural cellulose particles impregnated with an emulsified oily disinfectant derived from coal tar.

15. The method of making a dentifrice powder, comprising a chemically neutral and stable non-structural cellulose hydrate which method consists in subjectin viscose to the action of calcium chlorid an sodium bisulfite, removing water from the resulting gelatin-like cellulose hydrate material, breaking it up, repeatedly washing until neutral under the iodin test, drying until the resultant particles consist of a translucent horn-like substance, then powdering and finally impregnating with an antiseptic.

16. The method of making a dentifrice powder comprising translucent horn-like particles of substantially non-structural cellulose hydrate, which method consists in changing viscose to a gelatin-like mass, expelling water from the gelatin-like material and breaking up the mass to form a finely sub-divided precipitate, washing the precipitate to purify t e material and render it approximately neutral or slightly alkaline, drying the particles until no longer definitely wet to the touch, and impregnating the material with the desired antiseptic or medicament.

17. The method of making particles of precipitated, substantially non-structural cellulose hydrate, which method consists in changing viscose to a gelatin-like mass, expelling water from the gelatin-like material and breaking it up into particles and washing the particles.

18. The method of making a dentifrice comprising particles of precipitated, substantially non-structural cellulose hydrate, which method consists in changing viscose to a gelatin-like mass, expelling water from the gelatin-like product to form a finely subdivided precipitate, washin the precipitate render it approximately proximately neutral or slightly alkaline,

drying the particles until no longer definitely wet to the touch, and impregnating the material with an emulsified antiseptic or medicament. I

19. The method of making a dentifrice comprising translucent. horn-like particles of substantial non-structural cellulose hydrate, which method consists in changing viscose to a gelatin-like mass, dehydrating the jelly-like mass to form a granular or curd-like 'precilpitate, washin the precipitatc to purify t neutral or slightly alkaline, drying, grinding and screening the particles, and compounding the resu ting powder comprising .e material an render it apwith the other ingredients required to make the desired denti rice. I

20. The method of making a dentifrice consists in changing viscose to a gelatin-like mass, removin water to produce a curd-like finely subdivi ed precipltate, washin the prom itate and utilizing it as the mec anical c eaning ingredient of the desired dentifrice. o 4

Signed at New York city, in the county of New York and State of New York, this 19th day of December, 1917.

WILllIAM F. SPIES. HERBERT D. PEASE.

articles of substantially non structural ce lulose hydrate, which method 

